What's Confusing: I have a layered file, the color space assigned to it is sRGB. I save a png file via Save For Web, tick the option to convert export to sRGB. All looks good in the save for web 2-up preview. But when I open the new png file, it's color profile is set to Adobe RGB, and the color space looks off—not like it did in the SFW preview.

Details: My default color space is Adobe RGB. Sync'd across all CS5 apps. I have the option ticked to warn me on profile mismatches when opening a file. So far so good.

So it seems like my Working Space color (Adobe RGB) is overriding SFW settings as well as my document color space settings

but you can "assign" a working one when opening it in PS, but you need to change your prefs: edit>colour settings> under color management settings check profile mismatches ask when pasting and ask when opening. Then open the file

So within save for web there is no specific option for PNG embedded profiles, only to save as sRGB. Jpeg does give the option to embed a profile. BUT...

I still feel something is acting newly wrong here. My original psd file's color settings are being ignorored, as well as the sRGB option. Both for PNGs and JPEGs. All I'm doing is saving an sRGB file out, and that color setting is being stripped and defaults to my wroking color space. Is this standard functionality? Seems very wrong.

What settings file might I try and delete, besides the Photoshop general prefs...?

Saving out a PNG through Save For Web will strip the profile. The checkbox converts the numbers to sRGB, but the profile itself is stripped. So when you reopen this untagged file, the working space is assigned.

A regular Save As PNG, however, will keep the profile, although the "embed profile" checkbox is grayed out.

This is just how the current PNG implementation in Photoshop works. It makes no sense, but there it is. What you're seeing is in fact the standard "normal" behavior.

As for jpeg, the default with Save For Web is also to strip the profile, but here you at least have a choice to embed (you don't with PNG).

An update here. I may still be missing something, but this is what I get in this new scenario.

RGB layered file tagged with the Adobe RGB (1998) space. Export this via scripts/layer comps to files. This is different than SaveForWeb, as I can include the ICC here.

Select PNG 24, include ICC profile, and save.

When I open these files, there is no profile warning message—as it is the same color. But the color is off. The only way to get the color to match the psd is to convert to the same Adobe RGB profile it is already tagged with. The 'Assign Profile' command (even though it's the same) has no effect.